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1 2019

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Thermal Degradation Behaviour and Kinetics of aged TNT-based Melt Cast Composition B

Singh Arjun, Sharma Tirupati Chander, Singh Vasundhara, Mukherjee Niladri

Central European Journal of Energetic Materials

2019

Vol. 16, no. 3

360--379

In the present paper, three kinds of aged and freshly prepared 2,4,6-trinitrotoluene (TNT) based Composition B stockpiled, for a period of 20 and 32 years, were investigated for the effect of natural ageing on their thermal degradation behaviour and kinetic parameters. The properties investigated indicated that there was no significant change in the thermal stability of the samples aged under natural environmental conditions. The kinetic parameters were studied by means of the Kissinger method using the peak temperature at maximum reaction rate from DSC data, and the isoconversional Kissinger-Akahira-Sunnose (KAS) and ASTM E689 methods from TGA data. The apparent activation energies calculated by the Kissinger method were 173.8 kJ·mol–1 for fresh, 170.4 kJ·mol–1 for 20 y old and 187.1 kJ·mol–1 for 32 y old Composition B, respectively. The values calculated by the KAS method were found to be in the range 77.2-235.8 kJ·mol–1 for fresh Composition B, 75.7-224.0 kJ·mol–1 for 20 y old and 70.4-196.0 kJ·mol–1 for 30 y old Composition B, respectively. The activation energies obtained from the KAS methods are in good agreement and consistent with the isoconversional ASTM E689 kinetic method. The thermodynamic parameters, such the Gibbs free energy of activation (ΔG#), activation enthalpy (ΔH#) and activation entropy (ΔS#) for the formation of activated complexes were also studied and are discussed.